US8858901B2 - Use of a KMgF3 compound for trapping metals in the form of fluorides and/or oxyfluorides in a gaseous or a liquid phase - Google Patents

Use of a KMgF3 compound for trapping metals in the form of fluorides and/or oxyfluorides in a gaseous or a liquid phase Download PDF

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US8858901B2
US8858901B2 US14/124,545 US201214124545A US8858901B2 US 8858901 B2 US8858901 B2 US 8858901B2 US 201214124545 A US201214124545 A US 201214124545A US 8858901 B2 US8858901 B2 US 8858901B2
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compound
kmgf
gaseous
liquid phase
equal
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Bertrand Morel
Lorraine Leite
Laurent Moch
Alain Demourgues
Romain Clarenc
Alain Tressaud
Etienne Durand
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Comurhex pour La Conversion de lUranium en Metal et Hexafluorure SA
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    • C—CHEMISTRY; METALLURGY
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    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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    • Y02C20/00—Capture or disposal of greenhouse gases
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Definitions

  • the present invention relates to the field of trapping of metallic species.
  • a magnesium and potassium trifluoride (called hereinafter the “KMgF 3 compound”) to trap metals present in the state of fluorides and/or oxyfluorides in a gaseous or liquid phase.
  • the invention notably finds application in the nuclear industry, in which it can advantageously be used to purify uranium hexafluoride (UF 6 ) present in a gaseous or liquid stream, with regard to metal impurities which are also present in this stream.
  • UF 6 uranium hexafluoride
  • the nuclear fuel cycle designates all the steps which, from extraction of the uranium ore to the storage of the waste, enable fuels to be provided to nuclear reactors in order to generate distributable electrical energy.
  • This cycle includes a step which consists in converting the uranium extracted from the mines, concentrated in the form of yellow cake, into uranium hexafluoride whilst giving it the degree of purity essential for the manufacture of nuclear fuels.
  • yellow cake may contain several thousands of ppm of impurities with volatile fluorides and/or oxyfluorides, in particular those of molybdenum (Mo), vanadium (V) and tungsten (W).
  • Mo molybdenum
  • V vanadium
  • W tungsten
  • the nuclear fuel cycle as it is implemented in France also includes a step intended to convert uranyl nitrate derived from the reprocessing of spent fuels into uranium hexafluoride with a view to re-using it as a raw material in the manufacture of new fuels.
  • the uranium hexafluoride resulting from this conversion must satisfy the requirements of the ASTM C787 standard.
  • the uranyl nitrate derived from the reprocessing of spent nuclear fuels itself also contains several tens of ppb of impurities with volatile fluorides and/or oxyfluorides, such as those of technetium (Tc), neptunium (Np) and plutonium (Pu).
  • magnesium difluoride is also able to retain titanium tetrafluoride (TiF 4 ), niobium pentafluoride (NbF 5 ), tantalum pentafluoride (TaF 5 ) and antimony pentafluoride (SbF 5 ), molybdenum hexafluoride (MoF 6 ) and technetium fluorides.
  • TiF 4 titanium tetrafluoride
  • NbF 5 niobium pentafluoride
  • TaF 5 tantalum pentafluoride
  • SbF 5 antimony pentafluoride
  • MoF 6 molybdenum hexafluoride
  • the use of magnesium difluoride to decontaminate uranium hexafluoride of technetium is moreover described in U.S. Pat. No. 5,826,163 (reference [1]).
  • the inventors therefore set themselves the general aim of finding a material enabling the impurities present in uranium hexafluoride derived from the conversion of yellow cake or of reprocessing uranyl nitrate to be trapped, and which has none of the disadvantages posed by magnesium difluoride.
  • this material should be capable of sufficiently trapping impurities present in uranium hexafluoride, in order for the latter to satisfy standard ASTM C787, but without however trapping uranium hexafluoride itself, or only slightly.
  • this material should be able to be used to purify uranium hexafluoride both when the latter is in a liquid phase and when it is in a gaseous phase.
  • the present invention proposes to use a KMgF 3 compound to trap metals present in the form of fluorides and/or oxyfluorides in a gaseous or liquid phase.
  • KMgF 3 compounds are able, when brought in contact with a gaseous or liquid phase, in which metals such as technetium, rhenium, vanadium, molybdenum, niobium, tantalum, antimony and titanium are present in the form of fluorides and/or oxyfluorides, to retain these metals very effectively.
  • KMgF 3 compounds are consequently of very particular interest for purifying uranium hexafluoride and, in particular, uranium hexafluoride resulting from the conversion of natural uranium or from the conversion of uranium derived from the reprocessing of spent nuclear fuels.
  • the KMgF 3 compound preferably has a surface specific area equal to or greater than 30 m 2 /g as determined by the Brunauer, Emmett and Teller method, better known by the name “BET method”, on this compound in a powder state. Indeed, the inventors observed that the trapping capacities of KMgF 3 compounds are better when the surface specific area of these compounds is at least this value.
  • the surface specific area of the KMgF 3 compound not to exceed 150 m 2 /g, the value above which its chemical stability starts to be compromised, which becomes a hindrance to its use in trapping metals.
  • the KMgF 3 compound therefore typically has a surface specific area ranging from 30 to 150 m 2 /g and, better still, from 70 to 120 m 2 /g.
  • the KMgF 3 compound may be used in the form of a free powder.
  • this compound should be in the form of solid elements obtained by methods conventionally used for transforming powders, of the agglomerate, granulates, pellet or comparable types.
  • a KMgF 3 compound in the form of pellets the largest dimension of which is equal to at most 3 mm and, notably, pellets the dimensions of which range from 2 to 3 mm, has proved to be particularly advantageous.
  • the KMgF 3 compound may be used alone or jointly with another compound known to have capacities for trapping chemical species and, in particular, fluorinated and/or oxyfluorinated metallic species.
  • the KMgF 3 compound may be used in combination with magnesium difluoride, in which case it is preferred that the mass fraction of the KMgF 3 compound in the KMgF 3 /MgF 2 blend is at least equal to 0.2.
  • the KMgF 3 compound is able to trap metals present in a gaseous or liquid phase in the state of fluorides and/or of oxyfluorides as soon as it is brought into contact with this phase.
  • This fluoridation treatment may be implemented by bringing the KMgF 3 compound into contact with either pure fluorine, or a blend including fluorine and one or more other gases chosen from among the inert gases such as, for example, dinitrogen or argon, and the fluorine-based gases such as, for example, a blend of fluorine, argon and hydrofluoric acid.
  • the fluoridation treatment may be accomplished by using a blend of fluorine, dinitrogen and hydrofluoric acid.
  • the fluoridation treatment may be undertaken at a temperature ranging from ambient temperature to 500° C., with preference for temperatures of between 200 and 300° C.
  • the KMgF 3 compound is preferably used, i.e. brought into contact with the gaseous or liquid phase, at a temperature ranging from 80 to 200° C., with the understanding that it may also be used at other temperatures and, notably, at ambient temperature, i.e. at the temperature prevailing in the environment in which it is planned to use it.
  • this contact action is maintained for a minimum period of 20 seconds, ranging, preferably, from 60 to 300 seconds in the case of a gaseous phase, and from 60 to 600 seconds in the case of a liquid phase, depending on the impurities.
  • the KMgF 3 compound useful according to the invention may be prepared by methods which are easy to implement.
  • this reaction leads to the production of KMgF 3 compounds with a high surface specific area, typically equal to or greater than 100 m 2 /g, as determined by the BET method.
  • the product obtained may consist solely of KMgF 3 , or of a blend of KMgF 3 and of MgF 2 .
  • a KF/MgF 2 ratio greater than 1.1 is required to obtain the product the characterisation of which by X-ray diffraction shows that it consists solely of KMgF 3 .
  • Another object of the invention is a method of preparing a KMgF 3 compound having a surface specific area at least equal to 30 m 2 /g and at most equal to 150 m 2 /g (as determined by the BET method), which comprises:
  • Another of its objects is a second method of preparing this compound, which comprises impregnating magnesium difluoride by an aqueous solution including potassium bifluoride and, possibly, hydrofluoric acid.
  • FIG. 1 is a schematic diagram of an experimental device which enabled the inventors to assess the ability of KMgF 3 compounds to be used as traps with regard to fluorides and oxyfluorides present in the gaseous phase.
  • FIG. 2 represents the X-ray diffraction spectrum of a KMgF 3 powder before this powder is used to trap rhenium hexafluoride.
  • FIG. 3 represents the X-ray diffraction spectrum of the powder the X-ray diffraction spectrum of which is illustrated in FIG. 2 , but after this powder has been used to trap rhenium hexafluoride and before it is brought back into contact with ambient air.
  • FIG. 4 represents the X-ray diffraction spectrum of the powder the X-ray diffraction spectrum of which is illustrated in FIG. 2 , but after this powder has been used to trap rhenium hexafluoride and after it has been brought back into contact with ambient air.
  • FIG. 5 represents the Fourier transform infrared spectrum (FT-IR) of the powder the X-ray diffraction spectrum of which is illustrated in FIG. 4 .
  • FT-IR Fourier transform infrared spectrum
  • the reactor is closed and then placed in a bracket enabling the pressure and temperature present in this reactor to be controlled.
  • the bracket is itself placed in a microwave oven which is sold by the company CEM with the commercial name Mars 5TM.
  • This oven which operates at a frequency of 2.45 GHz, is set to a power level of 300 W and programmed to reach a temperature of 150° C. in 5 minutes and remain at this temperature for 1 hour.
  • the synthesis product obtained at this stage is then centrifuged for 10 minutes at 5000 revolutions per minute (rpm) and then dried for 2 hours in a stove at 100° C. It is then calcinated for 5 hours at 300° C.
  • a product in powder form is then obtained, consisting of KMgF 3 , and having a surface specific area of 120 m 2 /g, as determined by the BET method.
  • the preparation of a KMgF 3 compound is accomplished by a method known as the “impregnation method”. It is undertaken according to the following protocol.
  • magnesium difluoride (MgF 2 ) of surface specific area equal to 80 m 2 /g is then added to this solution.
  • the suspension obtained in this manner is then stirred for 4 hours at 60° C., and then placed for 48 hours at an ambient temperature.
  • the resulting product is then dried at 100° C. in a stove, washed with 200 mL of water, centrifuged for 10 minutes at 5000 rpm, dried again at 100° C. in the stove and then calcinated for 5 hours at 200° C.
  • a product in powder form is then obtained, consisting of KMgF 3 , and having a surface specific area of 30 m 2 /g, as determined by the BET method.
  • the present example relates to a test intended to assess the ability of a KMgF 3 compound to trap TcF 6 , and to characterise the products resulting from the reaction of the KMgF 3 compound with technetium hexafluoride.
  • technetium is a radioactive element
  • the test is undertaken using rhenium hexafluoride which has the same chemical properties as technetium hexafluoride—since rhenium and technetium indeed belong to the same column (VIIB) of the periodic table of the elements or Mendele ⁇ ev's table—but is more stable than it.
  • This test consists in causing a gaseous stream of rhenium hexafluoride to flow over a sample of the KMgF 3 compound in a device which has been previously had all trace of moisture removed from it to prevent the rhenium hexafluoride from hydrolysing, and in then characterising by X-ray diffraction and by Fourier transform infrared (FT-IR) spectroscopy the compounds resulting from the reaction of the KMgF 3 compound with the rhenium hexafluoride.
  • FT-IR Fourier transform infrared
  • this device includes a detachable sample-holder 12 , which is positioned in the path of a pipe 14 , in which the KMgF 3 compound is intended to be placed.
  • Pipe 14 is fitted with two quarter-turn valves, respectively 16 and 18 , which are located either side of sample-carrier 12 , and which enable the latter to be isolated from the remainder of the device, notably in order to install it and to remove it.
  • End 14 a of pipe 14 is connected to a first circuit which enables the device to be supplied with rhenium hexafluoride firstly, and with argon secondly.
  • This first circuit includes:
  • Each of ends 14 a and 14 b of pipe 14 is connected to a second circuit which notably enables the device to be evacuated and, at the end of the test, enables any rhenium hexafluoride which has not reacted with the KMgF 3 compound to be eliminated.
  • This second circuit includes:
  • the device also includes a thermocouple 60 enabling the temperature present in the interior of this device to be controlled, and a manometer 62 , which is connected to pipe 36 by a pipe 64 fitted with a quarter-turn valve 66 , and which enables the pressure present in this second circuit to be controlled.
  • Sample-holder 12 consists of a series of stainless steel washers placed one after another, inside which the KMgF 3 compound is placed, and which are positioned between sintered nickel filters to prevent the powder from being conveyed outside this sample-holder, notably due to the vacuum.
  • the KMgF 3 powder Prior to the test the KMgF 3 powder is treated by a gaseous stream consisting 10% of fluorine and 90% of argon (v/v) for 5 hours.
  • the KMgF 3 powder has a surface specific area of approximately 100 m 2 /g, as determined by the BET method, an oxygen rate of 2.2% by mass and crystallite sizes of 16 nm, as determined with the Fullprof application. In addition, it has the X-ray diffraction spectrum which is illustrated in FIG. 2 .
  • the KMgF 3 powder prepared in this manner is introduced into sample-holder 12 in a dry atmosphere (i.e. in a totally dehumidified glovebox), to prevent the rhenium hexafluoride from hydrolysing.
  • the mass of KMgF 3 powder introduced into sample holder 12 is 67.7 mg.
  • traps 34 and 40 and also the vacuum pump, are isolated from the remainder of the device by closing valves 44 , 38 and 52 , and the device is once again in a static primary vacuum.
  • Valves 16 and 18 are closed to isolate the sample of KMgF 3 .
  • Valves 58 and 66 are also closed.
  • Valves 22 and 26 are opened to introduce the rhenium hexafluoride into the device at a pressure of 150 mbar (15 kPa), this pressure being controlled using manometer 32 .
  • Valves 22 and 26 are then reclosed, and valve 16 is then opened to put the sample of KMgF 3 in contact with the rhenium hexafluoride.
  • the contact time is 1 hour and this contact is made at ambient temperature.
  • valves 44 , 38 , 18 , 60 and 52 are opened in succession, to establish a dynamic vacuum for 30 minutes, and to eliminate all traces of rhenium hexafluoride which have not reacted.
  • Sample-holder 12 is then isolated by closing valves 16 and 18 , and the vacuum pump may then be stopped.
  • Sample-holder 12 is removed from device 10 and introduced into a glovebox in an inert atmosphere, in order to recover the powdered KMgF 3 which it contains. This powder is blue-grey in colour, whereas it was white before being introduced into sample-holder 12 . Its mass is 94.8 mg, which is equivalent to a 40% mass increase.
  • the powder obtained in this manner is characterised by X-ray diffraction, firstly in a dry environment, and subsequently after contact with the ambient air.
  • the spectra obtained are represented in FIGS. 3 and 4 .
  • the powder is also characterised by FT-IR and the spectrum obtained is represented in FIG. 5 .
  • FIGS. 3 and 4 show that the KMgF 3 powder has indeed trapped the rhenium hexafluoride, since at least two phases have been formed within this powder, namely:
  • FIGS. 3 and 4 show that, if the powder is put into direct contact with the ambient air after trapping of ReF 6 , since the K 2 ReF 8 phase and the other phases which are present are very unstable, they are crystallised in the form of KReO 4 .
  • rhenium in the form of KReO 4 may be characterised, as shown by FIG. 5 , by FT-IR, with the appearance of an adsorption band around 920 cm ⁇ 1 , corresponding to an Re—O bond.
  • the present example relates to a test intended to assess the ability of a KMgF 3 compound to purify the uranium hexafluoride present in a gaseous stream with regard to the technetium hexafluoride also present in this stream.
  • the molar ratio of the rhenium hexafluoride to the uranium hexafluoride is 1/5 ppm.
  • the test is undertaken using an experimental device which includes mainly and successively a capacity supplied by an intake of UF 6 and an intake of ReF 6 and in which the gases are blended, an absorption column heated by a heater cable connected to a temperature regulator, and in which the following are placed: the KMgF 3 compound, a cold trap enabling the gases to condense at the outlet of the column, a container enabling the gases condensed in this manner to be hydrolysed, and a vacuum pump.
  • the test is undertaken at 10° C. and at an initial pressure of approximately 200 mbar (20 kPa).
  • the mass of KMgF 3 compound used is 158 mg.
  • the time during which this compound is in contact with the gaseous blend is 158 seconds.
  • the content of the column containing initially the KMgF 3 compound is also hydrolysed to determine the quantities of ReF 6 and of UF 6 trapped by this compound.
  • the time during which the KMgF 3 compound and the gaseous flow are in contact is 55 seconds.
  • the experiment is undertaken at 100, 150 and 200° C.
  • the residual content of vanadium trifluoride oxide of the ReF 6 /UF 6 blend is, for its part, 30 ppm.
  • the time during which the KMgF 3 compound and the gaseous flow are in contact is 100 seconds.
  • the experiment is undertaken at a temperature of 100° C.
  • the gaseous stream contains only 0.3 ppm of molybdenum hexafluoride, which corresponds to a decontamination factor of 100.
  • a KMgF 3 compound to purify the uranium hexafluoride present in a liquid stream with regard to molybdenum hexafluoride and vanadium trifluoride oxide also present in the stream is assessed.
  • This blend flows at a speed of 0.01 cm/s and remains in contact with the pellets of KMgF 3 compound for 288 seconds.
  • the decontamination factor is equal to 3 and the proportion of uranium hexafluoride retained in the column is 0.6% by mass.

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FR1155055A FR2976281B1 (fr) 2011-06-09 2011-06-09 Utilisation d'un compose kmgf3 pour pieger des metaux presents sous forme de fluorures et/ou d'oxyfluorures dans une phase gazeuse ou liquide
PCT/EP2012/060875 WO2012168420A1 (fr) 2011-06-09 2012-06-08 UTILISATION D'UN COMPOSÉ KMgF3 POUR PIÉGER DES MÉTAUX PRÉSENTS SOUS FORME DE FLUORURES ET/OU D'OXYFLUORURES DANS UNE PHASE GAZEUSE OU LIQUIDE

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CN105854907B (zh) * 2016-04-19 2018-07-24 河海大学 一种铜掺杂的KMgF3钙钛矿型可见光响应催化剂及其制备方法和应用
CN110387473B (zh) * 2019-08-12 2021-05-18 中国科学院上海应用物理研究所 一种以三氟化氮为氟化剂氟化分离铀和钼的方法
CN113023783B (zh) * 2019-12-24 2023-04-14 中核新能核工业工程有限责任公司 一种堆后铀微量杂质净化方法
CN117165789B (zh) * 2023-10-27 2023-12-29 海朴精密材料(苏州)有限责任公司 一种钨化学气相沉积生产废气的资源化利用方法

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